Esters of Organic Acids

Cellulose acetate has replaced cellulose nitrate in many products, for example, in safety-type photographic films. When a solution of cellulose acetate in acetone is passed through the fine holes of a spinneret and the solvent evaporates, solid filaments are produced. Acetate rayon is prepared from threads of these filaments. Some applications and solvents of commercial cellulose acetate grades are summarized in Table 9-5. 

Because acetylation of cellulose proceeds in a heterogeneous system, the reaction rate is controlled by the diffusion of the reagents into the fiber structure. The quality of the cellulose raw material used for acetate rayon is 

Cellulose acetate is usually produced by the so-called solution process with exception of the fully acetylated end product (triacetate). In the solution process the pulp is first pretreated with acetic acid in the presence of a catalyst, usually sulfuric acid. The purpose of this activation step is to swell the fibers and increase their reactivity as well as to decrease the DP to a suitable level. Acetylation is then performed after addition of acetic anhydride and catalytic amounts of sulfuric acid in the presence of acetic acid. After full acetylation the final triacetate obtained is dissolved. This primary acetate is usually partially deacetylated in aqueous acetic acid solution to obtain a secondary acetate with a lower DS of about 2 to 2.5. 

The fibrous acetylation process is performed in the presence of a suitable liquid, such as benzene, in which the reaction product is insoluble and which thereby retains the fiber form. For fibrous acetylation vapor-phase treatment with acetic anhydride can also be used. Besides sulfuric acid, perchloric acid and zinc chloride have been used as catalysts. 

The acid-catalyzed acetylation of cellulose proceeds according to the following reaction formula  

---

Charles R. Fordyce, Cellulose Esters of Organic Acids. 309... 

It is not only the esters of organic acids which combine, in the manner of the ethyl acetoacetate synthesis , with the enolates of ketones and of esters an analogous behaviour is shown by the esters of nitrous and nitric, acids. The process which leads to the formation of isonitroso-and atinitro-compounds yields products fundamentally similar to those already described just as with ethyl acetate the group CO.CHs enters, so here, the NO- and N02-groups are involved, and enolise " exactly as does >O=0 ... 

In previous chapters, we discussed the hydrolysis of a number of esters of A-(hydroxymethyl)phcnytoin, namely esters of organic acids (7V-acyloxy-methyl derivatives, Sect. 8.7.3) or inorganic acids (Sect. 9.3.2). Hydrolysis of these potential prodrugs released 3-(hydroxymethyl)phenytoin (11.45), whose breakdown to phenytoin and formaldehyde was also investigated per se [79], The latter reaction followed pseudo-first-order kinetics. At pH 7.4, the f1/2 values were 4.7 and 1.6 s at 25° and 37°, respectively. The tm values decreased tenfold for each increase of pH by one unit, which, together with the absence of any buffer catalysis, indicates catalysis by the HO- anion. 

It was proposed by the duPont Co(Ref 3) to prepare flashless smokeless prop In ts from NC DNT, in which is incorporated ethyl palmttate or other esters of organic acids insol in water but forming a gelatinous mass with NC DNT at about 80°... 

---